Synthesis and optical properties of organic–inorganic hybrid semi‐interpenetrating polymer network gels containing polyfluorenes

Organic–inorganic hybrid semi‐interpenetrating polymer network (semi‐IPN) gels containing polyfluorenes (PFs) are synthesized by hydrosilylation reaction of joint and rod molecules in toluene, where PFs are poly(9,9‐dihexylfluorene‐2,7‐diyl) (PF6) or, poly(9,9‐dioctylfluorene‐2,7‐diyl) (PF8), joint molecules are 1,3,5,7‐tetramethylcyclotetrasiloxane (TMCTS), or 1,3,5,7,9,11,13,15‐octakis(dimethylsilyloxy)pentacyclo‐[9,5,1,1,1,1]octasilsesquioxane (POSS), and rod molecules are 1,5‐hexadiene (HD) or 1,9‐decadiene (DD). The semi‐IPN gels containing low molecular weight PF6 show higher photoluminescence efficiency (?_g) than the toluene solution of PF6L (?_s). The semi‐IPN gels composed of long rod molecule of DD and cubic joint molecule of POSS show the most effective increase in the emission intensity. The emission intensity of PF6L increases as formation of the network in the POSS‐DD semi‐IPN gel. The POSS‐DD semi‐IPN gels containing high molecular weight PF6 and PF8 also show the increase of emission intensity than those of the toluene solutions. The semi‐IPN synthesized in cyclohexane show syneresis and phase separation between network structure and PF chains. The semi‐IPN gels containing PF8 show emission peaks at 450 and 470 nm derived from β‐sheet structure of PF8. A systematic study clears correlation between emission property and network structure and/or composition of semi‐IPN gels. The semi‐IPN gels provide emissive self‐standing soft materials with high efficiency and in a narrow wavelength range emission. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 973–984     

Preparation and characterization of insulin-loaded acrylic hydrogels containing absorption enhancers

The objectives of this study were to prepare insulin-loaded acrylic hydrogel formulations containing various absorption enhancers, to perform in vitro and in vivo characterization of these formulations, and to evaluate the factors which affecting insulin availability on rectal delivery of insulin using this hydrogel system. The acrylic block copolymer of methacrylic acid and methacrylate, Eudispert, was used to make the hydrogel formulations. As absorption enhancers, 2,6-di-O-methyl-beta-cyclodextrin (DM-beta-CyD), lauric acid (C12), or the sodium salt of C12 (C12Na), were incorporated into the hydrogels. In an in vitro release test, the release rate of insulin from the hydrogels decreased as the polymer concentration of the hydrogel increased. The addition of C12Na to the hydrogel further increased the insulin release rate, which was greater at higher concentrations of the enhancer. A portion of the C12Na was found to remain bound to the acrylic polymer in dissolution medium. Serum insulin levels were determined at various time points after the administration of insulin solution or insulin-loaded (50 units/kg body weight) Eudispert hydrogels containing 5% (w/w) of C12, C12Na, or DM-beta-CyD to in situ loops in various regions of the rat intestine. The most effective enhancement of insulin release was observed with formulations containing C12Na. The bioavailability of insulin from the hydrogels was lower than that from the insulin solutions. Hydrogel formulations containing 7% or 10% Eudispert remained in the rectum for 5 h after rectal administration. However, the 5% (w/w) C12Na solution stained with Evan's-blue had diffused out and the dye had reached the upper intestinal tract within 2 h. Finally, the rectal administration of insulin-loaded hydrogels, containing 4%, 7%, or 10% (w/w) Eudispert and 5% (w/w) of enhancer (C12, C12Na, or DM-beta-CyD) to normal rats was shown to decrease serum glucose concentrations. The greatest effect was found with insulin-loaded 7% (Eudispert) hydrogel containing C12Na which having cosiderable large insulin release rate and bioadhesive characteristics.     

Photoinduced charge separation and charge recombination of fullerene bearing dendritic poly(amidoamine) with carboxylates at the terminal in aqueous media

Photoinduced charge separation of fullerodendrimers with carboxylates at terminal sites (C60 approximately COO-) has been found in aqueous media. Time-resolved transient absorption and fluorescence measurements of the fullerodendrimers demonstrated that charge separation takes place from the terminal carboxylate anion to the central excited singlet state of C60, generating C60*- approximately COO* with high quantum efficiency in aqueous solution. In the presence of viologen dication and a sacrificial donor, the persistent viologen radical cation was generated.     

Radioactive nuclides in the marine environment--distribution and behaviour of 95Zr, 95Nb originated from fallout

To investigate behaviour of 95Zr, 95Nb in the marine environment, various samples have been collected and measured by means of Ge(Li) gamma-ray spectrometry and/or radiochemical analysis during a period from 1974 to 1982 at coastal area of Tokai-mura, Ibaraki prefecture. Concentration of the nuclides in seaweeds increased remarkably after atmospheric nuclear detonation by P.R. of China, and the activity ratio between the nuclides changed by time was not fit well by the transient decay equation. Concentration variation in sea water was smaller than that in sea weeds, and the minimum change in sea sediment. Increase of concentration in these environmental samples was observed in chronological order of sea water, sea weeds then sediment after detonations, suggesting that the uptake of the nuclides by these sea weeds from sea water is faster than that via root. Observed concentration factors on the nuclides by sea weeds were calculated from the observed concentrations in sea water and sea weeds. Maximum values on 95Zr and 95Nb were 2110, 2150, respectively for Ecklonia cava and Eisenia bicyclis.     

Nickel-catalyzed enantioselective three-component coupling of bis-1,3-dienes, aldehydes, and dimethylzinc

Nickel-catalyzed three-component coupling of bis-1,3-dienes, aldehyde, and dimethylzinc was investigated. In the presence of catalytic amounts of Ni(acac)2 and PPh3, bis-1,3-dienes smoothly react with an aldehyde and dimethylzinc via intramolecular cyclodimerization of bis-1,3-diene moiety. The reaction proceeds through formation of a cyclic bis-allylnickel complex, insertion of an aldehyde, and addition of dimethylzinc to the resulting oxanickellacycle intermediate. An enantioselective coupling was also achieved by the use of a chiral monodentate phosphine ligand, H-MOP.     

Unexpected Thermally Stable,Cholesteric Liquid‐Crystalline Helical Polyisocyanides with Memory of Macromolecular Helicity

The achiral sodium salt of poly(4‐carboxyphenyl isocyanide) (poly‐ 1 –Na) folds into a one‐handed helix induced by optically active amines in water. The induced helicity remains when the optically active amines are completely removed, and further modification of the side groups to amide residues is possible without loss of memory of macromolecular helicity. Although the helical poly‐ 1 –Na loses its chiral memory at high temperature, helical polyisocyanides modified with achiral primary amines, which no longer have any chiral components, keep their memory perfectly even at 100 °C in N,N‐dimethylformamide in some cases and exhibit cholesteric liquid‐crystalline phases, thus providing a robust scaffold with heat resistance to which a variety of functional groups can be introduced.     

A new method for evaluating the bitterness of medicines by semi-continuous measurement of adsorption using a taste sensor

We describe a new method for the evaluation of the bitterness of medicines by semi-continuous measurement of adsorption using a multichannel taste sensor or 'electric tongue'. The bitterness of 10 basic medicines was evaluated by both the taste sensor and in human gustatory sensation tests with 11 volunteers. The sensor part of the taste sensor consists of eight electrodes made of lipid/polymer membranes. Three variables were obtained from the taste sensor data: sensor output (S), the change of membrane potential caused by adsorption, corresponding to aftertaste (C), and the ratio C/S. These variables were used to predict an estimated bitterness score in multiple regression analysis. Semi-continuous measurement of C (every 30 s up to 150 s) was adopted as an additional explanatory variable, and the attenuation rate of C was defined as C'. These data were also subjected to multiple regression analysis. The correlation coefficient (r) estimated for the bitterness score predicted by the taste sensor, using C' for channel 2 and C/S for channel 4, and the score obtained by human gustatory sensation, was 0.824. This value was greater than that obtained using C/S for both channels 2 and 4 (0.734). The method described in the present study seems to offer good predictability for the evaluation of bitterness.     

One-pot synthesis of metalated pyridines from two acetylenes, a nitrile, and a titanium(II) alkoxide

Four-component coupling process involving two acetylenes, a nitrile, and a divalent titanium alkoxide reagent, Ti(O-i-Pr)(4)/2i-PrMgCl, directly yielded titanated pyridines in a highly selective manner. The reaction can be classified into four categories: (i) a combination of an internal acetylene, a terminal acetylene, sulfonylnitrile, and the titanium reagent to yield alpha-titanated pyridines, (ii) a combination of an internal acetylene, a (sulfonylamino)acetylene, a nitrile, and the titanium reagent to yield alternative alpha-titanated pyridines, (iii) a combination of an internal acetylene, a (sulfonylamino)acetylene, a nitrile, and the titanium reagent to yield titanated aminopyridines, and (iv) a combination of an acetylenic amide, a terminal acetylene, a nitrile, and the titanium reagent to yield pyridineamides with their side chain titanated. Some of these reactions enabled virtually completely regioselective coupling of two different, unsymmetrical acetylenes and a nitrile to form a single pyridine. Synthetic applications of these reactions have been illustrated in the preparation of optically active pyridines and medicinally useful compounds.     

Low-Frequency Sub-Terahertz Absorption in HgII−XCN−FeII (X=S,Se) Coordination Polymers

Self-assembly Fe^II complexes of phenazine (Phen), quinoxaline (Qxn), and 4,4′-trimethylenedipyridine (Tmp) with tetrahedral building blocks of [Hg^II(XCN)₄]²⁻ (X=S or Se) formed six new high-dimensional frameworks with the general formula of [Fe(L)_m][Hg(XCN)₄]⋅solvents (L=Phen, m/X=2/S, 1 ; L=Qxn, m/X=2/S, 2 ; L=Qxn, m/X=1/S, 3 ; L=Qxn, m/X=1/Se, 3-Se ; L=Tmp, m/X=1/S, 4 ; and L=Tmp, m/X=1/Se, 4-Se ). 1 , 3 , and 3-Se show an intense sub-terahertz (sub-THz) absorbance of around 0.60 THz due to vibrations of the solvent molecules coordinated to the Fe^II ions and crystallization organic molecules. In addition, crystals of 1 , 4 , and 4-Se display low-frequency Raman scattering with exceptionally low values of 0.44, 0.51, and 0.53 THz, respectively. These results indicate that heavy metal Fe^II−Hg^II systems are promising platforms to construct sub-THz absorbers.